KR101485974B1 - Textile electrode and accumulator containing such an electrode - Google Patents

Abstract

The invention relates to an electrode comprising (a) an electron collector containing one or more transition metals from the groups 4 to 12 of the Periodic Classification of the Elements, and (b) a material that is electrochemically active, present on the surface of the electron collector in the form of a nano-structured conversion layer containing nano-particles or agglomerates of said nano-particles, wherein the nano-particles have a mean diameter of between 1 and 1000 nm, preferably between 10 and 300 nm, wherein said electrochemically active material contains at least one compound of the transition metal or transition metals present in the electron collector, characterized by the fact that the electrode is a textile formed by metallic wires or fibers. The invention also relates to a half-accumulator and an accumulator containing such a textile electrode.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a textile electrode, and a storage battery containing the same. [0002] TEXTILE ELECTRODE AND ACCUMULATOR CONTAINING SUCH AN ELECTRODE [

The present invention relates to a novel electrode based on a fabric made of a metal fiber and / or wire whose surface is a nanostructure, and a semi-battery and a battery containing the electrode.

As the market for portable electronic devices is remarkably leaning, interest in rechargeable batteries or battery fields is increasing. With mobile phones with dazzling growth, the sale of portable computers that grow at 20% per year creates new demands on the performance of their power supplies. It is also expanding into a variety of toy markets that are increasingly commonplace for camcorders, digital photography, CD players, wireless devices and rechargeable batteries. Finally, in the 21st century, there will be significant developments in electric vehicles, hybrid cars and hybrid electric vehicles that can be recharged in the power grid, as international regulations on pollutant emissions and greenhouse effects from heat engines become increasingly stringent. do.

Due to the birth of new electronic devices, there is a need to develop a flexible, foil-type battery that is compatible with the miniaturization of an object and has an increased autonomy. In the hybrid electric vehicle market for electric vehicles, hybrid cars and electric power supply networks, it is important to obtain a battery that is very competitive at the same price in order to be light, compact, safe and able to compete with existing power generation solutions.

The term "lithium metal" (or Li metal) generally refers to one or more materials in which the anode or cathode comprises a metal, the electrolyte comprises lithium ions and the cathode or anode electrochemically reacts reversibly with the lithium ≪ / RTI > As a substance that performs an electrochemical reaction with the lithium in a reversible manner, there is, for example, an insertion material containing or not containing lithium. The electrolyte includes lithium ions, regardless of whether it is a liquid or a polymer loaded with a lithium salt (in the latter case, it is generally called a dry polymer).

The term "lithium ion" (or Li ion) generally encompasses an insulator in which the cathode contains lithium, and the anode comprises one or more materials that undergo electrochemical reactions in a reversible manner with the lithium, Lt; RTI ID = 0.0 > lithium-ion < / RTI > Examples of the substance that performs an electrochemical reaction with the lithium in a reversible manner include lithium or an insertion material containing or not containing carbon. The electrolyte includes lithium ions regardless of whether it is a liquid or a polymer immersed in a liquid (in the latter case, generally referred to as a plastic electrolyte).

Lithium metal and lithium-ion technology can meet the needs of electric vehicles, hybrid vehicles and hybrid electric vehicles that can be recharged in the power supply grid, but considering the nature of the materials used, they are still expensive and insufficient in safety.

The specific energy density of the battery indicated by the battery of Wh / kg is the ratio of the specific energy density of the battery to that of an electric vehicle, such as an electric vehicle, a hybrid vehicle with electrical autonomy (rechargeable or otherwise) It remains an important limitation. Among the lithium ion types currently the best batteries have a specific energy density in the range of 100 to 120 Wh / kg, which is much more expensive for large scale applications.

French patent application FR 2 870 639 in the name of the present applicant is made up of a "nanostructured" electrochemically active material containing nanoparticles composed of a metal or a compound of metals, for example an oxide, forming an electron collector Layer is present on the surface of the electron collector. ≪ Desc / Clms Page number 2 > The specific structure of the electrochemically active material allows for improved performance in terms of power and non-energy density.

However, the specific energy density of these batteries is always limited, among other things, due to the limited specific capacity of the electrodes.

The specific energy density of these batteries, expressed in Wh / kg of battery, increases as a function of the specific capacity of the anode or cathode, which is represented by the Ah / kg electrode. In other words, an increase in the specific capacity of the cathode causes an increase in the specific energy density of the battery. The specific capacity of the cathode can be expressed as follows.

[Equation 1]

In the formula,

C _m is the specific capacity of the cathode (Ah / kg)

C _s is the surface capacity of the cathode (Ah / m 2)

S _geo is the geometric surface of the cathode (m2)

m_ is the mass of the cathode (kg).

The term "geometric surface" as used herein to describe a fabric electrode refers to a dimension on a macroscopic scale of a metal fiber. This geometric surface is independent of the structure of the fabric, i.e. the number, shape and size of the wires making up the fabric, or the size of the fabric weave. Therefore, the geometric surface reflects only the bulk of the fabric inside the battery.

The specific capacity of the cathode can be expressed as follows.

&Quot; (2) "

In the formula,

C_ is the capacity (Ah) of the cathode,

S _dev is the developed surface (m 2) of the cathode,

S _geo is the geometric surface of the cathode (m2).

As used herein, the term "front side" refers to the surface of a metal fiber on a micro scale, that is, the actual interface between the metal wire (electron collector) and the surrounding environment (before formation of the conversion layer) Represents the interface between the layer and the environment. This surface is expressed in m2.

The metal fabric is also characterized by its "specific surface", which is measured by the BET method and which corresponds to the ratio between "front" and "geometrical surface" expressed in m 2 / m 2.

Combining Equations (1) and (2) gives the following equation.

&Quot; (3) "

The ratio C_ / S _dev is related to the chemistry and thickness of the electrochemically active material present on the electrode. In fact, the ratio can be expressed as the product of the capacity per unit mass of active material (C_ / m _ma ) and the mass of active material per unit area (m _ma / S _dev ).

therefore:

The capacity per unit mass (C_ / _mma ) of the active material is proportional to the number of electrons involved in the reaction equation for the electrochemical reaction taking place at the electrode. This is determined by the chemical nature of the electrochemically active material.

The mass of the active material (m _ma / S _dev ) per unit area corresponds to the product of the thickness of the layer made of the electrochemically active material and the density of the active material. Thus, the density of the active material is determined by the method of making the active material that determines the chemical properties of the active material and the thickness of the layer.

The applicant of the present invention has proposed to use one of the electrodes of the lithium-ion or lithium metal-type battery as a metal fiber including a layer made of a nano-structured electrochemically active material as described in the above-mentioned patent application FR 2 870 639 And / or a wire (electronic collector), thereby increasing the specific capacity of the electrode for the battery, thereby increasing the energy density of these batteries.

When the fabric type structure is selected for one of the electrodes of the lithium ion or lithium metal battery, the chemical property of the layer made of the substantially active material and the predetermined thickness can be used as a function of the mass of the electrode per unit mass of the electrode and the electrochemical active material The area (S _dev / m -) of the interface between the first electrode and the second electrode increases considerably.

The subject of the present invention, therefore,

(a) an electron collector comprising at least one transition metal from Groups IV to XII of the Periodic Table, and

(b) an electrochemically active material present on the surface of said electron collector in the form of nanoparticles or nanostructured conversion layers comprising clusters of these nanoparticles

And an electrode for a lithium metal battery. Wherein the nanoparticles have an average diameter of 1 to 1,000 nm, preferably 10 to 300 nm, and the electrochemically active material comprises at least one compound consisting of transition metals or transition metals present in the electron collector, Wherein the electrode is a fabric formed from metal fibers and / or wires.

As described in the above-mentioned patent application FR 2 870 639, the present invention is a microstructure, and a nanostructured layer comprising nanoparticles of at least one compound of a transition metal present in the electron collector, Is a layer obtained through chemical or electrochemical modification of the surface of the substrate metal. Known advantages of such a conversion layer include good adhesion to the substrate of the surface layer formed in particular and excellent ease with which such a layer can be produced by simple processing of the initial metal. In addition to these known advantages, the metal surface processing technique has certain advantages associated with the fine-fabric structure of the electrode of the present invention. This advantage is due to the fact that during the formation of the electrochemically active material it is necessary to preserve the fabric structure of the electrode, i.e. not to cause it to disappear by closing the weave of the fibers. The method of forming an electrochemically active coating by depositing a coating on the surface of the fabric structure causes a serious risk of clogging of the apertures in the fabric, thereby offsetting the inherent advantages of such a fabric structure. The risk of the fabric pore closure is obviously increased as the pore size is smaller. When the active material is produced by forming the conversion layer, the risk that the fabric openings are closed is limited because no metal or any other material is introduced from outside, and the fine dimensions of the electrode (electron collector + active material) The diameter and spacing of the wire) are approximately equal to those of the fabric initially used.

The fabric made of the metal wire used to form the electrodes according to the present invention may be woven, non-woven or knitted. It is better to be woven.

The metal fabrics used to form the electrodes of the present invention are preferably formed from very thin wires that are relatively less separated from each other. In fact, the above BET specific surface (per square meter of geometric surface) is higher as the wire is thinner and the number of wires per unit surface is greater. However, the thinness of the wire can be limited by the ability of the metal or metal alloy used for wire drawing. Some metals and alloys, such as copper, aluminum, bronze, brass, and some steel alloys with chromium and nickel, are very suitable for wire drawing and can be obtained in the form of very thin wires and other metals or alloys, Wire drawing is more difficult and can only be achieved in the form of relatively thick wires with an equivalent diameter of several hundred micrometers.

Generally speaking, the equivalent diameter of the cross-section of the wire of the fabric electrode coated with the conversion layer made of the metal fiber or wire forming the initial fabric, or the active material is 5 탆 to 1 탆, preferably 10 탆 to 100 탆, Particularly 15 to 50 mu m. The term "equivalent diameter" is understood to mean the diameter of a circle whose area is equal to the cross-sectional area of the wire.

The small equivalent diameter of the wires forming the electrodes of the present invention allows the wires to advantageously limit the mass of the electrodes in terms of their use in the battery. Thus, it is advantageous that the electrode according to the invention, consisting of an electron collector coated with a conversion layer, has a unit area mass below the geometric surface of 1000 g / m 2, preferably 10 to 500 g / m 2.

As explained at the beginning, the main object of the present invention is to propose an electrode for a lithium ion or lithium metal battery having a maximum active surface (cost saving associated with metal raw material) and a minimum volume (miniaturization of a battery) for a minimum electron collector mass I want to. By using a metal fabric as described above, Applicants have found that the specific surface (expressed per unit surface) of the geometric surface of the electrode is from 2 to 100 m 2 / m 2, preferably from 20 to 80 m 2 / m 2, And an electrode having an overall surface area per mass of 10 ^-3 to 5 m 2 / g, and preferably 10 ^-2 to 3 m 2 / g.

The electrodes according to the invention are distinguished from those disclosed and claimed by the applicant in the above-mentioned patent application FR 2 870 639, mainly because this is a textile structure. With regard to the chemical composition of the electron collector and the conversion layer, the technical characteristics of the electrodes of the present invention are described in the present application, and there is no need to select from the metals and metal alloys that exhibit adequate wire drawability and weaving ability. FR 2 870 639, which is incorporated herein by reference.

In a preferred embodiment of the present invention, the transition metal (s) of the electron collector is selected from the group consisting of nickel, cobalt, manganese, copper, chromium and iron, preferably iron and chromium.

During the formation of the conversion layer to form the active material of the electrode according to the invention, these metals are converted into the compounds of the transition metal (s) by suitable methods as described in more detail below. This compound is preferably an inorganic compound and is advantageously selected from chalcogenides and halides, preferably chalcogenides (oxygen, sulfur, selenium, tellurium), and the metal compound present in the conversion layer is a metal oxide It is especially good.

In a particularly preferred embodiment of the present invention, the transition metal compound is a compound represented by the following formula:

[Chemical Formula]

M _x O _y

In the above formula, 1? X? 3, 1? Y? 5, preferably 1? Y? 4, and M is at least one transition metal. This compound is preferably a group formed by a spinelle structure AB ₂ O ₄ wherein A is at least one selected from the group formed by Fe, Mn, Cr, Ni, Co and Cu a transition metal, B is Fe, Cr and a transition metal at least one member selected from the group formed by Mn), and / or process kwiok seed (sesquioxide) M 'from the ₂ O ₃ (formula, M' is Fe, Mn, Cr, Ni, Co, and Cu).

The transition metal compound is in particular Cr ₂ O ₃ or a compound corresponding to the following formula:

[Chemical Formula]

Fe _{x '} Cr _y' Mn _{z '} O ₄

In the above formula, 0? X '? 1, 0? Z'? 1 and x '+ y' + z '= 3.

The valence of M is preferably 2 or 3, especially 3. The compound represented _by the formula Fe _{x '} Cr _y' Mn _{z '} O ₄ includes, for example, a compound represented by the following formula: Fe _x' Cr _{1 -x '} Cr ₂ O ₄ (wherein x' do.

As noted above, the conversion layer of the fabric electrode of the present invention is a "nanostructured" layer comprising nanoparticles having an average diameter of 1 to 1,000 nm, preferably 10 to 300 nm. Such nanostructured layers are distinguished by a coarse and porous structure and contain at least 50 wt%, preferably at least 70 wt%, of nanoparticles.

In the conversion layer of the fabric electrode, it is preferable that the nanoparticles are rearranged to form a cluster with each other. The average size of the clusters is 1 to 10,000 nm, particularly 10 to 3,000 nm. The porous structure based on the nanoparticle clusters can be identified, for example, by scanning electron microscopy.

It is preferable that the conversion layer (electrochemically active material) completely covers the surface of the electron collector, and the thickness is 30 nm to 15,000 nm, particularly 30 nm to 12,000 nm.

According to one particularly advantageous embodiment, the electron collector is a fiber formed from a chromium-containing alloy, such as an alloy of iron and chromium. The electron collector may be made of stainless steel.

After formation of the nanostructured conversion layer as described above, transition metal-based metal fibers which can be used as electrodes for lithium ion or lithium metal accumulators are known in the prior art and are described, for example, in the following trade names: plain square weave ), Twill square weave, plain weft rib, twill weft rib, plain wrap rib, twill wrap rib, .

The method of forming the nanostructured conversion layer is described in application FR 2 870 639. The process used in this document can be used without further pretreatment or modification to the metal fabric described above. The conversion process is, for example, a high temperature heat treatment in a reducing, neutral, oxidizing atmosphere. These treatments are known and commonly used by those skilled in the art.

For example, the treatment may be a treatment in hydrogen at a temperature in the range of 500 to 1,000 占 폚, preferably 600 to 800 占 폚, for example at a temperature of about 700 占 폚 for 1 hour to 16 hours.

Further, the treatment may be treatment in air at a temperature in the range of 600 to 1,200 ° C, preferably 800 to 1,150 ° C, for example, at a temperature of about 1000 ° C for 1 minute to 16 hours.

The conversion layer formed at the end of the oxidation or reduction heat treatment is generally not a clear nanostructured structure sought for the inventive fabric electrode. The final nanostructuring of the electrode, i. E., The formation of nanoparticles, occurs only during the first discharge of the battery. It is of course possible to carry out the discharge to the fabric electrode before incorporating the fabric electrode into the lithium battery. This first discharge can be carried out, for example, at a low electric current density (geometric surface of the electrode of 0.05 to 5 mA / cm 2) of the fabric electrode to a lithium electrode in the organic electrolyte containing the lithium salt to a potential of 20 kV And then oxidizing the fabric electrode to a potential of 3000 mV against the lithium at a low current density (geometric surface of the electrode of 0.05 to 0.5 mA / cm 2).

The subject of the present invention is also an electrochemical half-cell and an electrochemical battery containing a fabric electrode as described above.

The electrochemical half-cell according to the present invention comprises a fabric electrode with a nanostructured conversion layer as described above, said fabric electrode having a coating that ensures that its entire surface acts to separate said battery electrode . This coating is designed to electrically isolate the two electrodes of the battery. Further, since this separator should be able to be immersed in a liquid electrolyte containing at least one lithium salt, it is preferably a porous structure or polymer structure which can be swollen by the electrolyte. In order to preserve the high specific surface that results directly from the fabric structure of the electrodes of the present invention, i. E. Large non-capacity and energy density, the deposition of the separating film is carried out in such a way that this fabric structure always appears in the semi- It is essential. In other words, it is preferable that the apertures or the structure of the metal fabric forming the electrode should not be closed due to the deposition of the separator and that at least 50%, in particular at least 70%, ideally all of the apertures in the initial metal fabric should be preserved . Closure or preservation of these openings depends, inter alia, on the thickness of the deposited separation film. The thickness of the separation membrane should be sufficiently small so that at least a portion of the pores of the fabric electrode are not closed by the separation membrane.

The deposition of such a separation film can be carried out by various suitable methods such as dipping, spraying or chemical vapor deposition, but the deposition of this coating is carried out by electrochemical means, in particular by a technique known under the name cataphoresis . The technique of introducing the metal structure or wire to be coated as a cathode into an aqueous solution containing the main component of the film to be deposited is very thin and even and continuous deposition which covers the entire surface of the structure with a very complicated surface shape . In order to be able to move toward the cathode, i.e. the structure or wire to be coated, the component to be deposited must be positive. For example, a method is known in which a cationic monomer is used to form an insoluble polymer film on the surface of the cathode after deposition and polymerization.

In a preferred embodiment of the semi-accumulator of the present invention, the separation membrane is deposited from an aqueous solution containing cationic monomers comprising the cationic monomer, preferably a quaternary amine functional group, by electrophoresis.

In a preferred embodiment of the semi-battery of the present invention, the separation membrane is deposited by electrophoresis from the aqueous solution onto a fabric electrode surface having a nanostructured conversion layer as described above. However, the separation membrane may be formed of a metal having a nanostructured conversion layer as described above from the aqueous solution by electrophoresis before the metal fiber or wire is assembled, for example, by weaving or knitting techniques to produce a fabric structure. The state of being deposited on the fiber or wire surface is also conceivable.

The above-described semi-accumulator formed by the fabric electrode coated with the separator includes, in addition to the semi-accumulator, a liquid electrolyte for immersing the separator in the semi-accumulator, and a polarizer The electrode may be contained in an electrochemical battery for the purpose of the present invention including an electrode which completely covers the surface of the immersed separator.

In a preferred embodiment of the present invention,

(I) the aforementioned half-cell comprising an anode with a separation membrane,

(Ii) a lithium salt-containing liquid electrolyte for immersing the separation membrane of the half-

(Iii) a mixture containing a lithium ion-inserting material, a polymer binder and a secondary electron conductor as a cathode and covering the surface of the separator immersed by the electrolyte, and

(Iv) a collector of current from the cathode made, for example, of aluminum

A lithium ion battery.

Liquid electrolytes containing lithium salts for use in lithium ion batteries are known to those skilled in the art. Examples of the lithium salt include LiCF ₃ SO _3, LiClO ₄ , LiN (C ₂ F ₅ SO ₂ ) ₂ , LiN (CF ₃ SO ₂ ) ₂ , LiAsF ₆ , LiSbF ₆ , LiPF ₆ and LiBF ₄ . The salt is preferably selected from the group formed by LiCF ₃ SO _3, LiClO ₄ , LiPF ₆ and LiBF ₄ .

Generally, the salt is dissolved in an anhydrous organic solvent which is generally composed of a mixture of propylene carbonate, dimethyl carbonate and ethylene carbonate in various ratios. Thus, the electrolyte generally comprises one or more cyclic or acyclic carbonates, preferably cyclic carbonates, as is known to those skilled in the art. For example, the electrolyte consists of LP30, a compound commercially available from Merck, containing EC (ethylene carbonate), DMC (dimethyl carbonate) and LiPF ₆ salt, 50% by weight / 50% by weight.

The cathode of the lithium ion secondary battery, for example a known _{manner, LiCoO 2, LiFePO 4, LiCo} 1/3 Ni 1/3 Mn 1/3 O 2 or LiMn ₂ O ₄ lithium ion insertion of one or more such material, or LiMX ₂ wherein M is a transition metal and X is a halogen atom.

In contrast to what has been described above, in order to deposit the separating film on the surface of the fabric electrode, the fabric structure of the electrode can always be identified after the deposition of an electrode of opposite charge, especially a material forming the cathode of a lithium ion battery It is not necessary. That is, the material that forms the electrode whose polarity is opposite that of the fabric electrode fills at least a portion of the openings or tissues of the semi-accumulator, preferably the continuous type of sheet or an assembly of sheets Including one fabric structure.

In one particular embodiment of the battery of the present invention, the battery comprises a fabric structure providing the function of an electrode and a separator function, that is, the half-cell function, as well as a function of a collecting device for the opposite polarity electrode . The semi-battery function is then provided, for example, by a warp wire of the fabric structure, and the function of the current collector of the opposite polarity is provided by a weft wire, or vice versa. In this case, the warp wire has a nanostructured conversion layer and is a metal wire composed of at least one transition metal from the IV to XII group of the periodic table applied by the coating of the separating film as described above. The weft wire is a metal wire made of, for example, aluminum and capable of serving as a current collector for a positive electrode.

The subject of the present invention, therefore,

(I) at least one transition metal selected from the group consisting of (a) at least one transition metal from Groups IV to XII of the Periodic Table and having an average diameter of from 1 to 1,000 nm and at least one compound of the transition metal And the entire surface of which is covered with a separating film,

     (b) a metal wire suitable as a positive electrode current collector

A fabric structure including both of the fabric structure,

(Ii) a lithium salt-containing liquid electrolyte for immersing the separation membrane of the half-

(Iii) a mixture that covers the entire surface of the fabric structure (i) including a lithium ion inserting material, a polymer binder and a secondary electron conductor, and a separation membrane immersed by the electrolyte (ii)

A lithium ion battery.

In addition, the subject matter of the present invention is the use of batteries as batteries for hybrid cars (rechargeable or otherwise) of batteries, electric vehicles, portable devices and stationary applications.

Finally, the application of the present invention is a supercapacitor comprising a fabric electrode according to the present invention.

1 shows a top view (FIG. 1A) of a half-cell according to the present invention and a cross-sectional view (FIG. 1B) taken along one-dot chain line AA 'in FIG. 1A. Such a semi-battery 200 includes an electron collector 100 , generally in the form of a fiber, part of which is shown in Figure IA, with a layer 101 of active material on the surface of the collector. The layer made of the active material is prepared, for example, by heat treatment of the collector 100 in a high temperature air. The collector 100 is generally made of stainless steel. The chromium (Cr), iron (Fe), and manganese (Mn) constituting components of the collector 100 react with oxygen (O ₂ ) in the air to form a chromium oxide of a nanoparticle type. No external materials such as a secondary electron conductor such as carbon black, a binder or another metal are added. The separator film 102 on the surface of the collector 100 and the nanostructured conversion layer 101 is deposited in the form of a thin film that completely covers the surface of the wire of the metal fiber with the conversion layer, generally by an electrophoresis process. This coating 102 is deposited so as not to close the openings 103 of the fibers, which is well illustrated in FIG. 1A. This separator is characterized by its ability to be immersed in a liquid electrolyte for a lithium-ion battery.

Claims (21)

(a) an electron collector comprising at least one transition metal from group IV to XII of the periodic table, (b) an electrochemically active material present on the surface of the electron collector in the form of a nanoparticle or a conversion layer which is a nanostructure comprising a cluster of nanoparticles, The nanoparticles have an average diameter of 1 to 1,000 nm, Wherein the electrochemically active material is an electrode comprising at least one compound of the transition metal (s) present in the electron collector, The electrode is a fabric formed from a metal wire, The electrode has a geometric surface area area mass of less than 1000 g / m < 2 & Wherein the electrode is a geometric surface of an electrode having a specific surface of 2 to 100 m < 2 > / m < 2 & Wherein the electrode is an electrode having a surface area of 10 < ^-3 > to 5 m < 2 > / g per unit mass of the electrode. The electrode of claim 1, wherein said fabric formed of a metal wire is a woven, non-woven or knitted fabric. The electrode according to claim 1, characterized in that the equivalent diameter of the cross section of the wire of the fabric electrode coated with the conversion layer made of an active material is 5 탆 to 1 mm. delete delete delete 4. Electrode according to any one of claims 1 to 3, characterized in that the transition metal (s) of the electron collector is selected from the group consisting of nickel, cobalt, manganese, copper, chromium and iron. The electrode of any one of claims 1 to 3, wherein the transition metal compound (s) is selected from chalcogenides and halides. 9. The electrode of claim 8, wherein the transition metal compound (s) is selected from oxides. 10. The method of claim 9, The transition metal (M) compound (s) are those of the formula M _x O _y , Wherein 1? X? 3 and 1? Y? 5 in the formula M _x O _y . 11. The method of claim 10, Wherein said transition metal compound is selected from those of the formula Fe _{x '} Cr _y' Mn _{z '} O ₄ and Cr ₂ O ₃ , Wherein 0? X '? 1, 0? Z'? 1 and x '+ y' + z '= 3 in the formula Fe _x' Cr _{y '} Mn _z' O ₄ . The electrochemical device according to any one of claims 1 to 3, characterized in that the electrochemically active material completely covers the surface of the electron collector in the form of a conversion layer having a thickness of 30 nm to 15,000 nm. . The electrode according to any one of claims 1 to 3, characterized in that the electron collector is made of stainless steel. The fabric electrode according to any one of claims 1 to 3, wherein the entire surface is covered with a separator, Wherein the thickness of the separation membrane is sufficiently thin such that at least a portion of the opening of the fabric electrode is not closed by the separation membrane. 15. The electrochemical half-cell of claim 14, wherein the separation membrane comprises a cationic polymer. (I) a semi-accumulator according to claim 14, (Ii) a liquid electrolyte for immersing the separation membrane of the half-cell, (Iii) an electrode which has a polarity opposite to the polarity of the half-cell and completely covers the surface of the separator immersed by the electrolyte, ≪ / RTI > 17. The method of claim 16, (i) a lithium salt-containing liquid electrolyte for immersing the separation membrane of the half-cell, (ii) a mixture comprising a lithium ion inserting material, a polymer binder, and a second electron conductor, as a cathode, covering the surface of the separator immersed by the electrolyte, (iii) a collector of current from the cathode Lt; / RTI > The half-cell comprising an anode with a separation membrane, Wherein the electrochemical battery is a lithium ion battery. (I) a nanoparticle comprising (a) at least one transition metal from group IV to XII of the periodic table and having an average diameter of from 1 to 1,000 nm and at least one nano- A metal wire having a function as a negative electrode, the metal wire having a conversion layer as a whole and having an entire surface covered with a separator,      (b) a metal wire as an electron collector for a positive electrode A fabric structure including both of the fabric structure, (Ii) a lithium salt-containing liquid electrolyte for immersing a separation membrane of a half- (Iii) a mixture that covers the entire surface of the fabric structure (i) including a lithium ion inserting material, a polymer binder and a secondary electron conductor, and a separation membrane immersed by the electrolyte (ii) And a lithium ion battery. An ultra-high capacity capacitor comprising the electrode according to any one of claims 1 to 3. 18. The electrochemical cell of claim 17, wherein the lithium ion battery is used as a battery for a hybrid vehicle, an electric vehicle, a portable device, and a political industry. The method of claim 9, wherein the transition metal (M) compound (s) A spinel structure represented by the formula AB ₂ O ₄ , and a sesquioxide M ' ₂ O ₃ , The expression from the AB ₂ O _4, A is Fe, Mn, Cr, Ni, Co and a transition metal at least one member selected from the group consisting of Cu, B is at least one member selected from the group consisting of Fe, Cr and Mn Transition metal, Wherein M 'is at least one transition metal selected from the group consisting of Fe, Mn, Cr, Ni, Co and Cu among the above M' ₂ O ₃ .

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